Alcohol and process of obtaining the same from carboxylic compounds.



UNITED v STATES PATENT OFFICE.

LOUIS BOUVEAULT AND GUSTAVE BLANO, OF PARIS, FRANCE.

ALCOHOL AND PROCESS OF OBTAINING THE SAME snom'onnnoxymc COMPOUNDS.

Specification of Letters Patent.

Patented Oct. 15, 1907.

Application filed January 28, 1904. Serial No. 190,347-

carboxylic groups existing in certain organic molecules into groups- GH OH characteristic of alcohols.

Our process of preparation of this class of alcohols permits of obtaining them directly in a state of purity and of preparing in large quantities certain alcohols which have heretofore only been able to be prepared in small quantities.

The general method hitherto used for preparing primary alcohols are not practically applicable either because of the insufficiency of the yield or because of the rarity or high cost of the parent materials.

We have discovered a new simple and practical method whereby monohydric and polyhydric alcohols may be produced in a regular manner and with very satisfactory yield.

This method consists essentially in transforming the carboxylic grouping GO H into the alcoholic grouping- OH OH by treating the amido and ether derivatives of the acids by sodium and absolute alcohol:

...oo.os os,os R and B, being al- GO.NH CH OH coholic radicals as CONRR GH .OH methyl, ethyl The novelty of our method resides in the fact that, the esters and the amide whose tendency to suffer r'eduction in this way had not been suspected hitherto, are reduced to corresponding alcohols by sodium in presence of absolute alcohol; the conditions of the reaction maybe varied according to the case in point,

and the example hereinafter given'should be regarded as a mode of operation and not as a type to be rigorously followed.

The presence of small quantities of water has a disastrous effect on the yield, probably because a part of the ester is then saponified and escapes reduction; for

this reason it is of the utmost importance, in order to obtain satisfactory yields to use perfectly absolute alcohol and esters deprived of every trace of moisture. The following example is given as an instance of the mode of operation which may be adopted in most cases.

Into .a vessel connected at the top both with a powerful reflux condenser and a dropping funnel there are introduced 6 atomic proportions of sodium in large pieces; there is then run in from' the'funnel one molecular proportion 'of the ester or the amid of the acid to be reduced mixed with i times its weight of absolute ethyl alcohol or a homologue thereof. The rate of fiow into the vessel is regulated so that there may be an energetic reaction without overtaxing the condenser, When all the liquid has been added the reaction is completed by heating for several hours by means of a water-bath or a bath of calcium chlorid;

if at this moment the sodium has not completely disappeared a little more alcohol is added. Finally, the whole is allowed to cool and a little water or dilute alcohol derived from a former operation is added and the mixture is distilled to recover the major portion of the ethyl alcohol which is ultimately converted into absolute alcohol. This ethyl alcohol sometimes carries over the alcohol sought andmust then rigorously fractionated. -The alkaline liquid left in the vessel contains the original acid in the form of a sodium salt and the alcohol corresponding with this To isolate this alcohol it may be distilled over in steam.

At the same time, if the alcohol is'sufiiciently soluble Alcohols of the Fatty Series. 3* I mum ALconou,

I. SATUBATED Atconons. BY m M1101! Boiling point Density 75 I B D Em 1 nhenylaoe- I m I egg-21s; me at 15 Ale h oiling int ensl n 18 9.110 ure- By Naming Po Phenylacetsunide.. y 1 tg gaemelts 8' Fol-mete 96-07a.t12.... 30 5 Ethyl butyrate Butenol 1 nfirgalgggl 0.82310 Acetate 107409 at 12 I was at 5e eeeee Eth 1va1erate..... Pentanol 1 138-139" 0.829 1 Ethgl n. pemeite Hexanol 1 15a" ease 8* g g 85 01'081 I010 10 Etyhltiisiice m r m eth yh pen- .160-165- 0.836 no" E513! gfifif it 12mm- 1007 at ore y 180 u ano momma y g ge gf' g Ethyl methylpro- Methyhpen- Mil-148 0.337 at 0 5 90 pylaeeto acetate tenoh +13 M 15145'5 t m 15- Ethyl ootenoate... Ootenoll 116 set-15 mm 0.838/0 Y m a $231??? +Vs1erate 159-161 at is th o u mm. I I 'gf yloctyl 75 mm Ethhyal +Parahrnrtl'i- Btu-266 Metizng 95 20 Octyl acetate... 98et15mm.. "5%; Y i

v Octyl butyrete 242-244 1 1 t 3 1554579 n Ootylvalemte. x Ethyl 11:25:18,119 or Nti namil 11...... 0.842/0 non orme 9...... y Acetate 10o atSmm. Pflmmc +Butymte.... 134-137" at 14 I +valemteuun 5 12 By reducing Alcohols Boiling point Density 100 mm. '30 Ethyl decanoete... DecenolI 120at12mm. Melts +8 Ethyl dimethyl 3.7 +3.7 dimethyl- 115-126 at 15 0.849/0" Ethyl a. c-Dime- +2.2 Dimethyl 123 at 10111111.

Ooteneoete octan'ol 1 mm. thylsuccinete butanediol Ethyl B. B. hexyl- +Methylzno- 111-116 at 14 Ethyl a. a-Dime- +2.2 Dimethylmethyl ecrylete nanol'l mm. thy utarete ntamedloli-t Ethyl laurete...... Dodecanoll 255259 Methy adlpete exane (11011.6 Melts st 105 Acetate... Acetate 140 rt 10 mm. Methyl 5 -methyl- +2 Methyl hex- 160-165" at 15, +Butyrate..... 162-164 at 10 ediimte anediol mm. mm. Ethy subemte.... +Oetsne diol 172 atZOmm. Melts at 40 +Velerate 170' at 10mm. 1.8 63 11 Ethyl myrlstate... Tetredecanol 1 160 at 10mm. Melts +38 Ethyleebacete..... +{J gene d1 p1 179 at 11 mm. Mal igs et IL mama Awouom The alcohols above described obtained by our method are industrially applicable because they can I I be used either directly or as esters in perfumery, con- 115 BY Naming Bmng "Density iectionery, distilleries, and like industries, or as parent E ml t materials for the preparationoi compounds (aldehydes,

th 1 lacetate Pen 1104011... .142 O.863 at 0 0 e609, ctenso mm. 1 1 e 0 Ethyl unddcyle- +Undecylen 10 150-152" at 30 n us 1 ese 5 es ow .scope Eggtel mm 1 th I Io m5 t 17 process and the applications to which it can be ap- 120 C en- Lme E ace ate diec1ad'1e fl8 'mm. o I IIIh d t th i f fth i u 0 ur me 0 permi s e orma. 1011 o e W0 0 ow-' Eth 1 cit llden A1 1119...... 15o-155 15- aceate e51: co 0 m, mg-alcohols which are of similar structure and which 55 lii' mfiemiff 1 at 20 we claim specially: the 3.7 drmethyl octanol 1 and the Ethyl oleate Oleic 81901101.... 207at13mm. 0.862 no 3.7 dimethyl 6 octenol 1. These alcohols are practi- 125 Ethyl a. and 5 cy- Cyclo-ertryliden 138-145 at 16 0.935 at 20 clocitrylidenapeetm i I cally obtained by condensation of synthetlc methyl 6 heptanone 2 or natural methyl 6' heptenone 2 with ethyliodecetat, by elimination of H 0, in the thusformed ether of oxy acid and finally by reduction of 11L Hmmcnuc m Tmmmc 'Awoxom I the ether of unsaturated acid by sodium and absolute 130 alcohol. These alcohols, which are particularly useful in erfumery, have the following characteristicsz-Al- By reducing Alcohols BOlllIlg point D fl y cohol 3.7 dimethyl octanol 1 is a colorless liquid at or- E 1 h ah dinary temperatures, 'and has a. boiling point of to, t 2 3; I 'figg gzgigi g f i g 0946 at degrees C. at 15'.mi1l1meters pressure, a s pecl fic 1 65 3 gene Mp. I gravity of 0.852 at 18 degrees (1.; and a refraction mmhg campholg- +EI fi i 211.213 14593 dex of 1.4401 for the line D. Its pyruvic ester boils at +Aoetat 135436 at 21 I to degrees C. at 15 to 16 nnlhmeters pressure,

70 I mm. and gives a. semi-carbazone melting at 124 degrees C.

, -Alcohol 3.7 dimethyl 6 octenol 1 is a. colorless liquid 140 Ethyl campmmw" at ordinary temperatures, and has a boiling point of 108 to 112 degrees C. at 10 millimeters pressure, a specific gravity of 0.858 at 19 degrees C.-, and a specific gravity of 0.8762 at 0. degrees 0., and has a refraction index of 1.4506 for the D line. Its pyruvic ester boils at 143 degrees C. at 10 millimeters pressure, and gives a semi-carbazone melting at 112 degrees C. Although we have herein claimed specifically the alcohol 3.7 dimethyl octanol 1 it is to be understood that we regard as included in our invention, alcohol 3.7 dimethyl 6 octenol 1.

What we claim is:

1. The process of transforming a carboxylic group into an alcoholic group, consisting in subjecting a herein described ether derivative of said carboxylic group to the simultaneous action of an alkali metal and absolute alcohol.

2. As an article of manufacture, the alcohol 3.7 dimethyl octanol, being a colorless liquid at ordinary temperatures,

and having a boiling point of 115 to 120 degrees C. at.

15 millimeters pressure, having a specific gravity of 0.852

at 18 degrees 0., having a refraction index of 1.4401 for 20 this 12th day of January 1904, in the presence of two 25 subscribing witnesses.

LOUIS BQUVEAUL'I. GUSTAVE BLANQ Witnesses JULES ARMENGAUD, Jenna, HANSON C. Coxn. 

